Phenoxy-substituted ortho-nitroanilines and ortho-phenylenediamines

ABSTRACT

New nitraniline and phenylene diamine compounds are disclosed. The compounds have the following structure   WHEREIN ONE OF Y1 and Y2 represents nitro or primary amino and the other represents hydrogen or halogen; each of Z1 and Z2 represents hydrogen or halogen; R represents lower alkyl, halogeno lower alkyl, lower alkoxy, lower alkylthio or halogen; X represents oxygen or sulfur; and m represents an integer of from 0 to 5. These compounds are obtained by reacting a compound of the formula   IN THE PRESENCE OF A STRONG INORGANIC BASE WITH A HALOGEN-2NITROANILINE OF THE FORMULA   WHEREIN ONE OF THE TWO Z&#39;&#39;s represents halogen, the other Z, Z2 and Y represents hydrogen or halogen, and p represents the integer 1 or 2. If the phenylene diamine product is desired, the resulting nitraniline can be reduced to the corresponding amino derivative.

[22] Filed:

United States Patent [1 1 Frick et al.

[ 5] Oct. 21, 1975 PHENOXY-SUBSTITUTED ORTHO-NITROANILINES ANDORTHO-PHENYLENEDIAMINES [75] Inventors: Wilhelm Ernst F rick,Pfeffingen;

Anton G. Weiss, Basel; Thomas Wenger; Walter Traber, both of Riehen, allof Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

May 30, 1972 21] Appl. No.: 257,724

Related US. Application Data [62] Division of Ser. No. 851,524, June 30,1969, Pat. No. 3,673,209, which is a division of Ser. No. 570,159, Aug.4, 1966, Pat. No. 3,506,767.

[30] Foreign Application Priority Data OTHER PUBLICATIONS Passerini,Chemical Abstracts, Vol. 45, pp. 7975-7976 (1951).

Barry et al., Chem. Abstracts, Vol. 45, p. 9501b (1951).

van der Grinten (1), Chem. Abstracts, Vol. 62, p. 1777b (1965).

van der Grinten ([1), Chem. Abstracts, Vol. 60, p. 4290c (1964).

Primary Examiner-Elbert L. Roberts Assistant ExaminerS. P. WilliamsAttorney, Agent, or FirmFrederick H. Rabin ABSTRACT New nitraniline andphenylene diamine compounds are disclosed. The compounds have thefollowing structure wherein one of Y and Y represents nitro or primaryamino and the other represents hydrogen or halogen; each of Z and Zrepresents hydrogen or halogen; R represents lower alkyl, halogeno loweralkyl, lower alkoxy, lower alkylthio or halogen; X represents oxygen orsulfur; and m represents an integer of from 0 to 5. These compounds areobtained by reacting a compound of the formula in the presence of astrong inorganic base with a halogen-Z-nitroaniline of the formulawherein one of the two Zs represents halogen, the other Z, Z and Yrepresents hydrogen or halogen, and p represents the integer i or 2. Ifthe phenylene diamine product is desired, the resulting nitraniline canbe reduced to the corresponding amino derivative.

7 Claims, No Drawings PHENOXY-SUBSTITUTED ()RTHO-NITROANILINES AND()RTHO-PHENYLENEDIAMINES This is a division of application Ser. No.851,524, field on June 30, 1969 now US. Pat. No. 3,673,209, which inturn is a division of application Ser. No. 570,159, filed on Aug. 4,1966, now US. Pat. No. 3,506,767.

The present invention relates to a new process for the production of1,2-nitranilines, 1,2-phenylenediamines, benzimidazoles, particularly2-halogeno or 2-halogeno alkyl-substituted benzimidazoles; to compoundsobtained by this process, compositions containing benzimidazoles, and toprocesses for the protection of organic material, particularlykeratin-containing material, by treatment with such active substances.

For the production of aryloxy-1,2- phenylenediamines, up to the presentonly the synthesis of 3-phenoxy-1,Z-phenylenediamine described by M.Oesterlin [Monatshefte 57, 3144 (1953)] has been known. This processprogresses by more than 5 steps to the difficulty identifiable endproduct. The second amino group is obtained by reduction ofasubsequently introduced nitro group into the aminodiphenyl ether. H. A.Scarborough [Soc 132, 2361-2367 (1929)] describes the care necessary anddifficulties encountered in the nitration. Halogenations of nitro-,aminoand acetamidodiphenyl ethers are also known from this publication;these however, only lead in each case to the monohalogen compound or totar products. Phenoxy-1,2-nitranilines or 1,2-phenylenediamines whichare mono' or poly halogenated have not been described up to the present.

It is also known that aromatic nitro compounds react on heating witharomatic primary amines in an alkaline medium to form azoxy and azocompounds.

Surprisingly, it has now been found that good yields of aryloxy andarylthio 1,2-nitranilines and, from these, the correspondingl,2-phenylenediamines are obtained in a very pure state when a metalsalt of an optionally non-inogenically further substituted monoor polynuclear phenol or thiophenol is reacted with a 3- or5-halogen-2-nitroaniline which can contain other nonionogenic, inertsubstituents and, if desired, the nitro group in the aryloxyorarylthio-2-nitroaniline is reduced to the amino group.

A particular embodiment of the present invention concerns the productionof 1,2-nitranilines and of 1,2- phenylenediamines of the general formulaI Y NH In this formula:

one of the symbols Y and Y represents the nitro group or the primaryamino group, the other represents hydrogen or halogen,

Z and Z each represent hydrogen or halogen,

R represents lower alkyl, halogeno-lower alkyl, lower alkoxy or loweralkylthio, halogen, particularly chlorine or bromine,

X represents oxygen or sulfur,

m represents an integer of from 0 to 5.

These compounds are obtained by reacting a compound of the generalformula 11 (III) (z) wherein one of the two Z's represents halogen, theother Z and Z and Y represent hydrogen or halogen and p is 1 or 2 and ifdesired, reducing the nitro group in the condensation product to theamino group.

The preferred temperatures for the condensation lie within the range of100 to 200C. It is of advantage to the progress of the reaction if theinorganic base is added as concentrated aqueous solution. The principalbases are the hydroxides of alkali and alkaline earth metals. Thecondensation can be accelerated by the addition of catalysts such ascopper.

The reduction of the nitro group to the amino can be performed by theusual methods, e.g. with catalytically activated hydrogen in thepresence of metal catalysts such as Raney nickel palladium etc, withnascent hydrogen by means of base metals and acids, with stannous saltsin acid solution etc. Preferably the reduction is performed by Bechampsmethod, i.e. with pulverised iron in weakly acid aqueous solution.

By the new process, the compounds of general formula I are obtained inyields of and in a state almost pure enough for analysis. Thus,laborious purification operations are not necessary. It is particularlysurprising that, for the reaction with the phenolates or mercaptides.the amino group of the halogen-2- nitraniline has not to be protected byacylation. On the contrary, tests have shown that onusing correspondinghalogen-nitro-N-acetyl anilines, the yield on saponification of theacetylamino group, drops to about 30%.

The compounds according to the invention are valuable intermediateproducts for the production of pharmaceuticals, pest control agents,optical brighteners and dyestuffs. For example, 1,2-phenylenediaminesare used for the production of blue fluorescentbis-benzimidazol-Z-yl-ethylenes which, as valuable optical white shades,have become of industrial importance. On condensing1,2-phenylenediamines with l,4,5,8- naphthalene tetracarboxylic acid,valuable vat dyestuffs are obtained. 1,2-nitranilines are valuable diazocomponents for the production of ice dispersion and pigment dyestuffs.

According to a second aspect of the invention, the abovementioned1,2-nitranilines and 1,2-phenylene diamines are preferably used asintermediates for the production of 2halogeno benzimidazoles of theformula l\/' C Hal (IV) DIP-Z wherein R is hydrogen, halogen, ortrifluoromethyl;

Hal is halogen. preferably chlorine or bromine,

R, is hydrogen or a metal cation,

X is oxygen, sulfur, sulfinyl, or sulfonyl,

Z is halogen, nitro, hydroxy, mercapto, alkyl of up to 6 carbon atoms,alkoxy of up to 6 carbon atoms, alkylthio of up to 6 carbon atoms,trifluoromethyl. lower alkyl-substituted amino, benzoylamino, halogenobenzoylamino, trifluoromethyl benzoylamino, benzene sulfonylamino,halogenosulfonyl-amino, alkylsulfonylamino, alkylsulfinyl,alkylsulfonyl, trifluoromethyl benzenesulfonylamino, trifluromethylhalogeno benzenesulfonylamino or the radical of sulfonic acid and itssalts, ester and amide forms,

m is an integer offrom l to 5, and

p is an integer of from O to 3.

These 2-halogen benzimidazoles have excellent insecticidal andacaricidal activity, particularly however, marked activity againstinsects and their stages of development, such as moth larvae and alsofur and carpet beetle larvae, which injure keratin material. Due totheir affinity to keratin fibers, the 2-halogenbenzimidazole derivativesof general formula I draw onto these fibers from aqueous dispersionsand, if R, is hydrogen, also from aqueous solutions of their salts, and,in this way, the keratin material treated therewith is protected frominjury caused by the larvae of clothes moths and other moths as well asthat caused by larvae of fur and carpet beetles (Anthrenus andAttagenus).

These compounds are also active, however, against other insects,including termites, as well as mites and are thus used for general pestcontrol, particularly for industrial application in the protection ofplants and, in particular, material, e.g. for the protection of organicmaterials such as paper, Wood, textiles, synthetic materials etc.against attack by insects and mites.

The compounds with a halogenated phenoxy group, are of particularinterest.

The new 2-halogeno benzimidazoles are prepared according to theinvention, by reacting a 2-hydroxybenzimidazole of the formula V (Z) P N@x@ c 01-1 (v) wherein R, X, m, Z and p have the same meaning as definedabove, for instance, with phosphorus oxychlo ride (POCl or phosphorusoxybromide (POBroptionally, in the presence of hydrochloric acid orhydrobromic acid and, if desired, transforming the 2- halogenobenzimidazoles so obtained into their salts.

[Helv. chim. acta 44, 1278 (1961); J. Chem. Soc. 1963, 2934; Gazz. ital.88, 13 (1958)]. The production of 2-hydroxy benzimidazoles serving asstarting material by various usual processes is also described in thesecitations.

Alternatively, 2-mercapto-benzimidazolels may be used as startingmaterial for the production of 2- halogeno benzimidazoles. The new2hal0geno benzimidazoles are then obtained by:

a. oxidizing such starting materials with a suitable oxydizing agentsuch as potassium peremanganate to form the corresponding 2-sulfonicacid derivative and reacting this with phosphorus pentachloride orphosphorus oxychloride to form the instable sulfonic acid chloride whichdecomposes into the corresponding 2- chlorobenzimidazole [Annalen derChemie 647, 5-7, (1961) describe similar reactions], or

b. treating such starting materials with chlorine in the presence ofwater and, if desired another solvent, and, if desired, transforming the2-halogen-benzimidazoles obtained according to (a) or (b) into theirsalts. [Similar reactions are described in J. Am. Chem. Soc. 72, 4890(1950)]. Carbon tetrachloride and, particularly, glacial acetic acid,are used, e.g. as solvents for this reaction.

When the oxidative chlorination of nuclear unsubstituted2-mercapto-benzimidazole is performed in acetic acid at room temperaturefor a longer time (Shours) then, with simultaneous chlorination of thenucleus, a mixture of 2,5,6-trichloro-benzimidazole and 2,5,6,7-tetrachlor-benzimidazole is formed [Knobloch and Rintelen, Archiv. derPharmazie 291 (63. Vol.) pages 180-184 (1958)].

The 2-mercapto-benzimidazoles which can be used as starting materials inthe modified process according to the invention, can be obtained byknown processes, e.g. by reacting correspondingly substituted 0-phenylenediamines with carbon disulfide, thiophosgene or thiourea, Theo-phenylenediamines necessary for these reactions can be produced intheir turn by the process of the present invention as described above.

If desired, phenylthio-1,2-phenylenediamines can be oxidized by knownmethods to obtain phenylsulfinyl-or phenylsulfonyl-l ,2-phenylenediamines.

According to a third aspect, the present invention relates to new2-trifluoromethyl benzimdiazoles processes for their production andcompositions containing such Z-trifluoromethyl benzimidazoles.

2-Trifluoromethyl-benzimidazoles which contain at least one phenylradical bound to the benzo ring by way of an oxygen or sulfur atom, thesulfinyl or sulfonyl group, have not been known up to the present. Ithas now been found that such compounds containing the substituentmentioned in the 4(7)- and/or 5(6)- position, in which the phenylradical itself in unsubstituted or can be substituted by ionogenic ornon-ionogenic groups, have excellent pesticidal properties and are thusvaluable for the control of pests of all types.

The 2trifluoromethyl benzimidazoles of formula VI 2)nIl wherein Rrepresents a halogen atom having an atomic weight below 100, or ahalogenoalkyl radical,

R represents a halogen atom having an atomic weight below 100 or a loweraliphatic hydrocarbon radical optionally bound by way of an oxygen orsulfur atom, the sulfinyl or sulfonyl group,

Z represents a halogen atom having an atomic weight below 100, hydrogen,lower alkyl, lower alkoxy, lower alkylmercapto;

R, represents hydrogen, or a metal cation;

X represents an oxygen or sulfur atom, the sulfinyl or sulfonyl group,and

m represents an integer of O to 3,

n represents an integer of O to 2,

p represents an integer from 1 to 3 and, if R H, also their salts, areof particular importance for the combatting of pests because of theirexcellent insecticidal, acaricidal and microbicidal (bacteriostatic andfungistatic) properties. The compounds have an excellent action oninsects particularly on the larvae of insects which eat keratin fibers,e.g. Tineidae and Der mestidae, so that they are particularly suitablefor the protection of keratin material.

In general formula VI of halogen atoms having an atomic weight below100, chlorine and bromine atoms are preferred. The trifluoromethylradical is the preferred halogenoalkyl radical R,. By lower aliphatichydrocarbon radicals, alkyl or alkenyl radicals having straight orbranched chains are meant those, such as the methyl, ethyl, allyl ormethallyl radical, the propyl, butyl or amyl radicals. In the case of Rthese radicals can also be bound, by way of an oxygen or sulfur atom,the sulfonyl or sulfonyl group, to the phenyl radical.

The new 2trifluoromethyl-benzimidazoles are produced according to theinvention by reacting a 1,2- phenylenediamine having at least one phenylradical bound by way of an oxygen or sulfur atom, the sulfinyl orsulfonyl group as substituent, with trifluoroacetic acid and/or with oneof its reactive functional derivatives.

The following compounds are meant by functional derivatives oftrifluoroacetic acid in the process according to the invention:trifluoroacetic acid anhydride, trifluoroacetic acid bromide andchloride. the esters, e.g. methyl, ethyl esters, as well as thecorresponding ortho esters and metal salts of trifluoroacetic acid, alsotrifluoroacetic acid amidine. The reaction can be performed simply withtrifluoroacetic acid alone or with one of the derivatives given above.It is preferred, however, that trifluoroacetic acid be used in thereaction together with one of these derivatives, eg. withtrifluoroacetic acid anhydride.

New benzimidazoles from the group embraced by 5 general formula VI arepreferably produced by reacting a 1,2-phenylenediamine of the generalformula (2) I (R u p 2 wherein R R Z, R.,, X, m, n" and 2' have themeanings given in formula VI, with trifluoroacetic acid andtrifluoroacetic acid anhydride and, optionally. in reaction products soobtained wherein R is hydrogen. converting them into the correspondingsalts with an inorganic or organic base.

To produce such salts of the new benzimidazoles, inorganic bases,particularly the hydroxides of alkali met als, or organic bases,particularly tertiary amines, are used. The water soluble salts are ofparticular importance as the application of the new active ingredientsis preferably made from aqueous media.

Benzimidazoles of general formula VI wherein R is a lower aliphatichydrocarbon radical or a benzyl or phenethyl radical optionallysubstituted in the nucleus by halogen, can be obtained also frombezimidazoles wherein R is hydrogen or from salts of such benzimidazolesby reaction with an alkylating or aralkylating agent, optionally in thepresence of an acid binding agent. Alkylating or aralkylating agents areesters of lower aliphatic or araliphatic alcohols with strong acids suchas halogen hydracids, sulfuric acid or aryl sulfonic acids. Inorganicbases, e.g. the hydroxides and carbonates of alkali and alkaline earthmetals or organic bases, particularly tertiary amines such astrialkylamines or pyridine are used as acid binding agents.

The 1,2-phenylenediamines used as starting materials for the processaccording to the invention can be produced from correspondingnitranilines by reduction according to Bechamps. These nitranilines canbe produced by condensation of metal salts of phenols and thiophenolswith halogen-nitrilines.

The condensation product with thiophenol, after acylation of the aminogroup, can then be oxidised to form the corresponding phenylsulfinyl orphenylsulfonyl acyl-nitraniles. Hydrogen peroxide, potassiumpermanganate or organic per acids such as peracetic acid are examples ofoxidizing agents.

The term "lower alkyl" as used, per se or in combination with othergroups, in the specification and appended claims means hydrocarbons withup to 6C- atoms like, for instance, methyl, ethyl, propyl, isopropyl,butyl etc.

The term lower alkoxy is used for an alkoxy group with up to 6 C-atomslike, methoxy, ethoxy, propoxy etc.

The following examples serve to illustrate the present invention withoutlimiting the same thereto. Where not otherwise stated, parts are givenas parts by weight. The temperatures are given in degrees Centigrade.

EXAMPLE 1 a. 48.2 Parts of 3,4,6-trichloro-2nitraniline are added to18.82 parts of melted phenol at and the whole is heated to At thistemperature, 11.2 parts of aqueous 50% potassium hydroxide solution areadded dropwise within 1 hour. The water is continuously distilled fromthe mixture. The reaction mixture is then heated for 6 hours at -150while stirring whereupon it is cooled to 100 and 300 parts by volume ofboiling water are added. The solution is then stirred for 3 hours andafterwards left to stand for 12 hours. 1500 parts by volume of water arethen added to the reaction mixture, then 50 parts by volume of 30%aqueous sodium hydroxide solution are added and finally it is stirredfor 2 hours. The precipitate formed is filtered off under suction,washed several times with water and dried in vacuo over NaOH. (Yield ofcrude product 65 parts 93.2% of the theoretical. M.P.

l13-1l5). After recrystallisation from ethanol, 4,6-dich1oro-3-phenoxy-2-nitraniline melts at 133-135. The yield of pureproduct is 41.5 parts (69.4% of the theoretical).

b. 14 Parts by volume of 80% acetic acid are added to 66 parts of ironpowder in 350 parts by volume of water at 80 and the mixture is heatedfor 15 minutes at 90- 1 At the same temperature, 59.8 parts of 46dichloro-3-phenoxy-2-nitraniline are added in portions within 1 hour andthe mixture is refluxed for 16 hours. After cooling to about 80, thereaction is made weakly phenolphthalein alkaline with 20 parts of sodiumcarbonate and 400 parts by volume of chlorobenzene are added. Afterbringing quickly to the boil it is filtered hot and the residue iswashed with hot chlorobenzene. The chlorobenzene phase is separated in aseparating funnel, washed with water, dried over sodium sulphate andevaporated to dryness in vacuo. The 4,6'-dichloro-3-phenoxy-l,2-phenylenediamine is obtained as an oil in the crude stateand is obtained in crystalline form from hot benzene/petroleum ether.The yield of pure product is 39.4 parts. M.P. 85-87.

EXAMPLE 2 a. 48.2 Parts of 3,5.6-trichloro-2-nitraniline are added to29.4 parts of melted 4-chlorothiophenol at 100 and the whole is heatedto 130. 11.2 Parts of aqueous 50% potassium hydroxide solution are thenadded dropwise to the melt within 1 hour. The amount of water added isdistilled off within 5 hours at a temperature of 130-145. The melt isthenstirred for another 4 hours at 145, then cooled to 100 and 200 partsby volume of hot water are added. The mixture is then left to stand for12 hours at room temperature. 1000 parts by volume of water and 50 partsby volume of 30% aqueous sodium hydroxide solution are then added andthe whole is stirred for 2 hours at room temperature. The crystallineprecipitate is isolated, washed several times with water and dried inthe air. yield of crude product: 65 parts (93.2% of the theoretical),M.P. 1131l5. Recrystallised from ethanol, 4,6-dichloro-3-(4-chlorophenylthio)-2-nitraniline melts at 119-120. Theyield of pure product is 49.5 parts 71% of the theoretical.

b. 14 Parts by volume of 80% acetic acid are added to 66 parts of ironpowder in 350 parts by volume of water and the mixture is heated for 15minutes at 90100. 69.8 Parts of 4,6-dichloro-3-(4-chlorophenylthio)-2-nitraniline are then added in portions within 2hours at the same temperature and the reaction mixture is refluxed for18 hours. The reaction is carefully made phenolphthalein alkaline with18 parts of sodium carbonate, the reaction mixture is cooled to 80 and,at this temperature, 400 parts by volume of chlorobenzene are added.After stirring for a short time, it is filtered hot. The residue iswashed with a little hot chlorobenzene. The chlorobenzene phase isseparated in a separating funnel, washed with water, dried over sodiumsulphate and then evaporated to dryness under water jet vacuum. Theyield of crude 4,6- dichloro-3-(4'-chlorophenylthio)-l,2-phenylenediamine is 62 parts; M.P. 1161 18 (sinters at 1 10).Recrystallised from benzene, the product melts at 1161 17 (yield: 48.2parts 75.5% of the theoretical).

From equivalent amounts of correspondingly substituted nitranilines andphenols or thiophenols, the phenoxy or phenylthio 2-nitranilines givenin the first column are obtained and 7 reduced to the 2-phenylenediamines given in column 2 by theprocesses described inexamples 1 and 2.

4,6-dichloro-344'-chlorophcnoxy-Z-nitranilinc. M.P. 127-1 294,6-dichloro-3(3',4- dichlorophcnoxy)-2nitranilinc.M.P.92-944.6-dich|oro-3-(2'.4'- dichlorophenoxy)-2-nitra ni|inc.M.P. l34l35 I v4.6dit:hloro-3-phenylthio-2- nitranilinc. M.P. l57-l594,6-dichloro-3-2'.5'- dichlorophenylthiu )-'lnitranilinc.M.P. 165-167"3.4-dichlorQ-5-(4-chlorophcnoxy)2-nitrannilinc 3.4-dichloro-5-(4 -chlorophcnnxy )-l .2-phenylenedia- M.P. l9()l92 mine, M.P. 104-106 4.4'-(3",4'-dichlorophenoxy )-5-chloro-1,2 phenylene diamine. M.P. 9597C.'5. 4-'(2',5-dichlorophenylthio)-5-chloro 1,2-phenylene-diamine. M.P.l60l62C. 6. 4-phenyl'thio-5-chloro-1,2-phenylene-diamine. M.P.

phenylenediamine. M.P. 7980C.

phenylencdiamine.

1 l. 3,5-dichloro-6-(4'-chlorophenoxy)-1,2 -phenylenediamine. M.P. 9799C.

12. 3,5-dichlo'ro-6'-phenoxy-1,2-phenylenediamine.

M.P. 85-87C.

Oil. H I 14. 3,5-dichloro-6-(4-chlorophenoxy)-1,2-phenylene-diamine.M.P. l161 17C.

15. 3 ,5-dichloro6-( 2,4-dic'hlorophenoxy)-1 ,2-

phenylenediamine. M.P. 1151l7C. I

16. 3 ,5-dichloro-6( 3 ',4'-dichlorophenoxy)-l ,2-

phenylenediamine. M.P. 107C.

17. 3 ,5-dichloro-6-( 2',3 -dichlorophenylthio)-1,2-

phenylenediamine. M.P. 166168C.

18, 3,5-dichloro-6-(4-bromophenoxy)-l ,2-

phenylenediamine. M.P. 82-84C.

19. 3,5-dichloro-6-(4-methoxyphenoxy)-l,2-phenylene-diamine. Oil.

20. 3,5-dichloro-6-(2,4,5'-trichlorophenoxy)-l ,2- phenylenediamine.M.P. 143145 C.

3 ,5-dichloro-6-( 3 -trifluorornethyl-4- chlorophenoxy )-l,2-phenylenediamine 1 17-1 20C.

' phenylcncdiamine.M.P.'l66 168 I 3,5-dichloro-6-phenylthio-1,2phenylenediamine.

9 22. 3,5-dichloro--(4'-chlorophenoxy)-l,2-phenylenediamine. M.P.l88l90C. 23. 3,5-dichloro-5-( 2,4'-dichlorophenoxy)-l ,2-

phenylenediamine. crude oil.

24. 3 ,5-dichloro-5-phenylthio-l ,2-phenylenediamine.

Oil. 23. 3,5-dichloro-5-( 3 ,4-dichlorophenoxy)1 ,2-

phenylenediamine. Oil.

26. 3,5-dichloro-5'(2,5-dichlorophenylthio)-l,2-

phenylenediamine. M.P. l84-l86C.

27. 3,5-dichloro-4(4'-chlorophenoxy)-1 ,2-

phenylenediamine. M.P. l43-l44C.

28. 3,5-dichloro.-4-(2',4-dichlorophenoxy)-l,2-

phenylenediamine. Oil.

3-bromo-4-(4-chlorophenoxy)-5-chloro-l ,2- phenylenediamine. M.P.156l57.5C.

30. 4-chloro-5-(4-chlorophenylsulfinyl)-l ,2-

phenylenediamine.

31. 4-chloro-5-( 4-chlorophenylsulfonyl)-l ,2-

phenylenediamine. M.P. l69-l72C.

32. 3,5-dichloro-6-(4'-chlorophenylsulfinyl)-l,2-

phenylenediamine. M.P. l90-192C.

33. 3,5-dichloro-6-(4-chlorophenylsulfonyl)-l ,2-

phenylenediamine. M.P. l40-142C.

EXAMPLE 3 15.2 parts of 2-mercapto-4,6-dichloro-7-(3,4-dichlorophenoxy)-benzimidazole [produced by condensation of3,5-dichloro-6-(3,4-dichlorophenoxy)- l,2-phenylenediamine with CS CSClor thiourea] are dissolved in 400 parts by volume of glacial acetic acidto which 35 parts by volume of concentrated hydrochloric acid and 2drops of concentrated HNO are added. At -25, a solution of 11.2 parts ofchlorine in 200 parts by volume of carbon tetrachloride are addeddropwise within 1 hour and the whole is stirred for 14 hours at 20. Thereaction mixture is then evaporated to dryness and made stronglyalkaline with concentrated NaOH (pH 11l2) whereupon the product almostcompletely dissolves. Undissolved particles are filtered off and the pHof the filtrate is adjusted to pH 4 with concentrated hydrochloric acidwhereupon the product precipitates. The precipitate is filtered offunder suction washed and dried at 60. The pure 2,4,6-trichloro7(3',4-dichlorophenoxy)-benzimidazole melts at ll6l22.

" EXAMPLE 4 12 parts of 4,6-dichloro-7-(3'-trifluoromethyl-4-chloro-phenoxy)2-hydroxybenzimidazole [produced by a condensation of3,5-dichloro-6-( 3 trifluoromethyl-4 -chlorophenoxy)-1,2-phenylenediamine with phosgene, urea or chlorocarbonic acid ester] in120 parts by volume of phosphorus oxychloride are boiled until a clearsolution is formed. A weak stream of hydrogen chloride is thenintroduced for 3 hours. After this time, the reaction mixture is cooledand the excess phosphorus oxychloride is distilled off in vacuo. Theoily residue is poured into 1000 parts of 20 cold water, and, afterstirring for 1 hour, is extracted with ether. The ether phase is washeduntil it is neutral, dried with sodium sulphate and evaporated.Recrystallised from toluene, the pure 2,4,6-trichloro-7-(3"trifluoromethyl-4-chlorophenoxy)- benzimidazole obtainedmelts at 234235.

EXAMPLE 5 7, 7 parts if 2, 4, 6 trichloro 7 (3, 4dichlorophenoxy)benzimidazole are dissolved in 80 parts by volume ofdimethyl formamide and, after the addition of some parts per thousand ofSeCl chlorine gas is added. The temperature is kept at 2530. Afterintroducing chlorine gas for 2 hours, the reaction mixture is pouredinto 500 parts of ice water and the precipitated resinous product isisolated and dissolved in 15 parts by volume of 30% NaOH with theaddition of 1000 parts of water. The somewhat opaque solution isfiltered and precipitated with concentrated hydrochloric acid.Recrystallisation from ethanol/water yields pure2,4,5,6-tetrachl0ro-7(3,4-dichlorophenoxy)-benzimidasole which melts at245-247.

EXAMPLE 6 7.7 parts of 2-mercapto-4,6'dichloro-7- phenoxybenzimidazoleare suspended in 150 parts by volume of concentrated hydrobromic acid(40%) and then, at room temperature, a solution of 16 parts of brominein 50 parts by volume of hydrobromic acid is added dropwise. The wholeis then stirred for 24 hours at 35*30. The reaction mixture is thenpoured into 1000 parts by volume of ice water, the product whichprecipitates is filtered off and washed with water. The residue isdissolved in IN sodium hydroxide solution, active charcoal is added, thesolution is filtered and the residue is precipitated by acidifying withconcentrated hydrobromic acid to pH 2-3. The resulting 2,5-dibromo4,6-dichloro-7-phenoxy-benzimidazole is filtered off, washeduntil it is neutral and dried.

EXAMPLE 7 2'Nitro-3-amino-4,4,6-trichloro diphenylether 56.7 g of2-nitro-3,4,6-trichloroacetanilide (German Pat. No. 178,299) are heatedtogether with 25.7 g of p-chlorophenol and 44.8 g of caustic potashsolution (50%) in an oil bath at l50160C for 16 hours while stirring.Volatile portions are distilled off thereby. After cooling to theobtained melt is poured into a mixture of2 I. water and 200 ml. 1 NNaOH. the mix ture is stirred at 25 for 30 minutes and the productfiltered off by suction. The crude material is recrystallized fromalcohol. The yield is 20.7 g (corresponding to 31.2% of the theoreticalyield). The ob tained 2-nitro-3-aminol4,4,6-trichloro diphenylethermelts at l25-127C.

2,3Diamino-4,4',6-trichlorodiphenylether ml of water are heated and 19.8g of iron powder added. The mixture is heated to 90C while stirring. 4.5ml of glacial acetic acid are added and the mixture stirred for another10 minutes at 90 to 95C. During the next hour, 20 g of2-nitro-3-amino-4,4,6-trichlorodiphenylether are added gradually andsubsequently 25 ml of alcohol. Stirring is continued throughout thenight while boiling under reflux. After cooling down the mixture, solidsodium carbonate is added until the mixture is alkaline tophenolphthalein. After the addition of ml of chloro benzene, the mixtureis heated to boiling and the insoluble parts are filtered off through achina clax filter while still hot. The organic phase is separated fromthe aqueous phase by means of a separating funnel. The organic phase isthen washed with water and dried over sodium sulfate. The obtainedchloro benzene solution is evaporated to dryness and the obtainedproduct recrystallized from alcohol. 15.6 g of2,3-diamino-4,4,6-trichlorodiphen- 1 1 ylether are obtained having amelting point of 97 to 99C.

2-Mercapto-4,6-dichloro-7-[4-chlorophenoxy]benzimidazole 15.2 g of2,3-diamino-4,4,6-trichloro diphenylether and 70 ml of alcohol areplaced in a flask and a solution of g of potassium ethyl xanthogenate inml of water is added. The mixture is heated to boiling under reflux for40 hours while stirring. While still hot, 150 ml of water are added andthe mixture adjusted to a pH of 6 by the addition of glacial aceticacid. After cooling, the precipitate is filtered off by suction andwashed with water. The crude product is dissolved in a mixture of 30 mlconcentrated NaOH, 30 ml alcohol, and 650 ml water. Insoluble materialis removed by filtration, and the filtrate acidified by the addition ofhydrochloric acid. The obtained precipitate is filtered off by suction,washed thoroughly with water and dried. 9.2 g of 2-mercapto-4,6-dichloro-7-[4-chlorophenoxy]benzimidazole are ob tained having a meltingpoint of 245 to 247C.

2,4,6'Trichloro-7-[ 4 "chlorophenoxy benzimidazole 9.2 g of2-mercapto-4,6-dichloro-7-[4-chlorophenoxylbenzimidazole are dissolvedin 250 ml of glacial acetic acid with warming and 25 ml of concentratedhydrochloric acid as well as 2 drops of concentrated nitric acid areadded. The mixture is cooled to 17C and chlorine passed in (up to atotal of 6 g) during 1 hour while stirring. Stirring is continued foranother 15 minutes. The reaction mixture is poured into 1 l of icewater, the precipitate is filtered off by suction and washed with water.The product is recrystallized from alcohol, then from benzene. 2.5 g of2,4,6- trichloro-7-[4-ch1orophenoxy]benzimidazole are obtained having amelting point of l 12120C.

The following compounds according to the invention may be produced inthe manners described in Examples 3 to 7.

TABLE II M.P. "C

1) 2.6dich1oro-5-phenoxy-bcnzimidazolc 240 242 2)2.6-dichloro-S-phenylmcrcapto- 243 244 benzimiduzolc 3)2.6-dichloro-5-(4'-chlorophcnoxy) 199 201 bcnzimidazolc 4)2.6-dichloro-5-(4-chlorophcnylmercupto) 207 208 bcnzimidazole 5)2.6dichloro-5-(4'-bromophcnoxy)- 193 195 bcnzimiduznlc 6)2.6-dichloro-5-(2.4-dichlorophcnoxy)- 216 218 bcnzimidazole 7)2.6-dichloro-5-(3'.4'-dichlorophenoxy)- 220 227 benzimidazolc 8)2.6.7-trichloro-5-(4-chlomphcnoxy)- 245tdcbcnzimidazolc comp osition 9)2.6.7-trichloro-5-(4'-chlorophcnylmcr- 273 275 cap1o)-bcnzimidazolc 10)2.6.7-trichloro-5-(2',5-dichlorophcnyl- 237 239 mercapttxbenzimidazolc 1l 2.6-dichloro-5-(4-methoxyphenoxy)- 201 203 bcnzimidazolc l2)2.4.6-trichloro-7-phenoxy-bcnzimidazole 173 179 13)2.4.6-trichloro-7-phenylmercapto- 197 205 bcnzimidazole 14)2,4,6-trichloro-7-(4'-chlorophenoxy 112 120 benzimiduzole l5)2,4.6-trichloro-7-(4'-chlorophenylmer- 213 216 capto)-benzimidazole l6)2,4.6-1richloro-7(4'-bromophenoxy)- 127 130 benzimidazole M.P. C

2,4.6-trichloro-7-( 2 ,4 dichlorophcnoxy)-bcnzimidazolc2,4,6-trich1oro-7-t 2 ,5 '-dich1orophenylmercapato )-bcnzimidazolc2,4.6-trichloro-7-( 2 .4,5 '-trichlorophcnoxy)-benzimidazole2,4,6-trichloro-7-( 4 -methoxyphen0xy benzimidazole 2,4,6-trichloro7-(4'-ch1orophenylsulfinyl) benzimidazole2,4,6-trich1oro-7-(4'-chlorophenylsulfinyl )-benzimiduzole2.4.6.7-tctrachloro-5-(4 '-chlorophcnoxy benzimidazole2,4,5,6-tetrachloro-7-( 4-chlorophcnylsulfinyl )-benzimidazole2,4,6-trichloro-5-bromo-7-(3 ,4 dichlorophcnoxy)-benzimidazole2.6-dichloro-4,7-dihr0m0-5-(4'- chlorophcnoxy)-benzimidazole2,4.6,7tctrachloro-5-( 2 ',4 dichlorophenoxy)-bcnzimidazole2,6dichloro-4,7-dibrom0-5( 2',4'- dichlorophenoxy)-benzimidazo1e2.4.6-trichloro-5-(4-chlorophenoxy benzimidazolc 2.4,6trichloro-5-(4-chlorophenylmercapto)henzimidazole 2.4.6-trichloro-5-( 2,4-dichlorophenoxy)-benzimidazole 2.4.6-trich1oro-5-( 2'.5dichlorophenylmercapto)-benzimidazole2,4,6-trichloro-5-(4-chloro-5'-trifluoromelhyl phenoxy)benzimidazole2,4,6-trichloro-S-( 2',4'.5 '-trichlorophenoxy)benzimidaz0le2,6-dichloro-4-brom0-S-(4'-chlorophenoxy)-benzimidazole2,6-dichl0r0-4-hromo-5-( 4'-chlorophenylmercapto)-benzimidazole2-chloro-5-phenylsulfamoyl-benzimidazole 2.4.6trichloro-5-(4'-ch1orophenyl sulfamoyl)-benzimidazole2.4.6-trichloro-5-( 3 '-trifluoromethyl-4- chlorophenylsulfamoyl)-benzimidazole 2,4,6-trichl0ro-5-( N-methyl-N-3 ',4'-dichlorophenylsulfamoyl)-benzimidazole2-chloro-5-(tetrachlorophenylsulfamoyl)-benzimidazole2-ch1oro-S-(4-chlorophenylsulfonylamino)-benzimidazole 2-chloro-5( 2-methy|-4 ',5 '-dichlorophcnylsulfonylamino)-henzimidazole2,6-dichlor0-5-mcthyl su|fonylaminobcnzimidazolcZ,6-dichloro-5'(4-chlorophenylsulfonyl )-benzimidazole2,4,6-trichloro-5-methylsulfonylamino-benzimidazole 2,4,6-trich1oro-5-(4'-chlorophenylsulfonylamino)-henzimidazo|e 2-chloro-4,6,7tetrabromo-5-methylsulfonylaminmbenzimidazole 2-ch1oro-5-( 3 -trifluoromethyl-4'-chloro-phenylsulfonylamino)-bcnzimidazole 2.4.6,7-tetrachloro-5-( 4'-chlorophenylsulfonylamino )-bcnzimidazole 2-chloro-5-(3.4'-dich1orobenzoylamino benzimidazole 2-chloro-5-( 2',4',5-trichlorobenzoylamino)-benzimidazole2,4-dichloro-5-(3,4dichlorohcnzoylamino)-bcnzimidazole2,6-dichloro-5(2,4,5-trichlorobenzoylamino)-benzimidazole mixture of2,4,6.7-tetrachloro and 30%2,4,6trichloro-5-(3',4'dichlorobenzoylamino)-benzimidazolc2-chloro-5-(3-trifluoromcthyl-4'- chloro phenylcarbamoyl)-benzimidazolecomp osition) 197 200 145 (decomposition 164166 comp osition) 228- 229190(decomp osition) (decomposition) 214 215 comp osition) 170(decomp Thecompounds of formula [V which are illustrated by examples 3 to 6 can beused according to the usual methods for textile finishing. They haveaffinity to keratin material and are excellently suitable, therefore,for the protection of such materials from injury by insects, inparticular they are suitable for the wash and light fast moth-proofingof such materials both in the crude as well as in the processed state,for example of raw or processed sheepss wool as well as other animalhairs, fells and furs. ln addition to the wash and light fastmoth-proofing in the dyebath, the compounds can also be used for theimpregnation of wool and woollen articles in dry cleaning processes, thematerials then becoming equally excellently moth proofed.

In addition to their insecticidal action on the larvae of the clothesmoth, the compounds of formula IV are also active against the larvae ofthe fur and carpet beetles. The textiles treated in any way desired withthe compounds according to the invention such as woollen blankets,woollen carpets, woollen underwear, woollen clothes and knitted goods,are given protracted protec tion from the usual types of insects whichare injurious to keratin material.

The agents used for the protection of keratin materials against injuryby insects should contain the active substances of formula IV in afinely distributed form. Thus, solutions, suspensions and emulsions ofthe active substances in particular are used.

The compounds containing a hydrogen atom in the heterocyclic ring (R,H), in the form of their alkali metal salts generally have good watersolubility. They can be applied to the keratin material direct fromthese aqueous solutions, either by dipping the material for a shorter orlonger time in the alkali metal salt solution, or spraying them with thesolutions, or by treating them in the solutions at a raised temperatureas in dyeing processes.

Because of their solubility in organic solvents, these compounds arealso particularly well suited for application from non-aqueous media.Thus, the materials to be protected can simply be impregnated with thesesolutions or, if a suitable solvent is chosen, the moth proof finishingcan be combined with a dry cleaning process.

Propylene glycol, methoxyethanol, ethoxyethanol and dimethyl formamidehave proved to be particularly suitable organic solvents. to which canbe added distributing agents and/or other auxiliaries such as soaps andaqueous sodium hydroxyde solutions. Emulsifying agents such as sulfatedricinus oil, sulfite waste liquor and fatty alcohol sulfates areparticularly mentioned distributing agents.

EXAMPLE 8 First, a 20% solution of 2,4,6-trichloro-7-(3,4'-dichlorophenoxy)-benzimidazole in glycol monomethyl ether is produced.10 Parts by volume of this solution are diluted with 200 parts by volumeofa solvent suitable for dry cleaning, e.g. a suitable benzine fraction(Diluan S"). If desired, other cleansing additives can be added. Thewoollen articles are then treated in Compounds used in the test thiscleaning liquor in the usual way and subsequently centrifuged to acontent of solvent of about 100% of the weight of the wool. Afterdrying, they provde to be mothproofed.

Baths of the same or analogous composition can also be used in ananalogous way for the moth proofing of untreated or already otherwisetreated or cleaned articles.

Similar mixtures can also be used for the spraying of wool in everystage of processing.

the insecticidal action of 2-halogen-benzimidazole derivatives accordingto the invention of general formula IV against insects which injurekeratin material was tested as given below, and the textile materialscontaining keratin which had been treated with these active substanceswere tested as to resistance to attack by insects which injure keratinmaterial in the following way:

Test Methods and Results:

A 0.5% stock solution of each active substance to be tested in ethyleneglycol monomethyl ether (methyl cellosolve) is prepared. Then an aqueousapplication liquor is prepared at room temperature which contains 20 mlof the stock solution mentioned (0.] g of active substance) in 400 mlliquor. 10 g of wool flannel are then well wetted with hot water andintroduced into the liquor at room temperature. While constantlycirculating the woollen sample, the bath temperature is raised to Cwithin 15 minutes, then 2% of 80% formic acid (calculated on the weightof the wool) are added and the treatment in the liquor is continued foranother 30 minutes at this temperature. It is then cooled, the woollensample is rinsed in running tap water, centrifuged and, for the purposeof drying, is hung up. The concentration of active substance is 1%,calculated on the weight of the wool.

The sample so dried is then subjected to the moth proofing test (injuryby clothes moth Tineola biselliella) according to the Swiss Associationfor Standardisation leaflet 95901 and also it is tested for fastness tothe fur beetle larvae (Attagenus piceus) and carpet beetle larvae(Anthrenus vorax) according to Swiss Association for Standardisationleaflet 95902; the method for Anthrenus larvae was simply applied toAttagenus piceus larvae in that 6-7 week old larvae of the latter typewere used for the test. Basically, the method consists in cutting fourequal sized pieces from the treated wool flannel sample and exposingeach of these pieces for 14 days at a constant temperature (28C) andconstant relative humidity to the attack (appetite) of 15 larvae of therelative pest (two pieces of material with the same pest).

The results are tabulated as follows:

xxxx very good protection 57: devoured material xxx good protection 5 to1571 devoured material xx moderate protection l5 to 50% devouredmaterial x insufficient protection 5071 devoured material Moths Atta-Anthrenus genus benzimidazole 2,6-dichloro-5-(2 ,4'-dichlorophenoxybenzimidazole 2,6-dichloro-5-(3 ,4-dichlorophenoxy)- benzimidazole2,4,6-trichloro5-(4'-chlorophenoxy)- benzimidazole XXXX XX XXXX XX XXXXXX XXX XXX XXX XXX Continued Compounds used in the test Moths Atta-Anthrenus genus 2,4,6-trichloro-7-phenoxy-benzimidazolc xxxx xxx xxx2,4,6trichloro-7-phcnylmercaptoxxxx xxx xxx benzimidazole2.5-dibromo-4,6-dichloro-7-phenoxyx xxxx xxx benzimidazole2,4,6-trichIoro-7-(4-chlornphenoxy)- xxxx xxxx xxx bcnzimidazole2,4.6-trichloro-7-(4'-chlor0phenylxxxx xxxx xxx mcrcaptn)-benzimidazole2,4.6-trichloro-7-(2'.5'-dichlorophcnylxxxx xxxx xxxmcrcapto)-bcnzimidazolc 2,4,6 trichloro-7-(2',4'-dichlorophenoxy)- xxxxxxxx xxx bcnzimidazole 2,4.6-trichloro-7-(3'.4'-dichlorophenoxy)- xxxxxxxx xxx bcnzimiduzole 2,4,6-trichloro-5-hmmo-7-(3',4-dichloroxxxx xxxxxxx phcnoxy)-benzimidazolc 2.4,S,6-tetruchlor'7-(3',4'-dichloro xxxxxxxx xxx phcnoxy)-henzimidazo|e2,4.5,6-tctrachloro-7-(4'-chlorophenylxxxx xxxx xxxsulfinyU-hcnzimidazole 2.6-dichloro-4,7-dibromo--(4'-chloroxxxx xxxx xxxphcnoxy)-benzimidazole 2,4,6,7-tctrachloro-5-(4'-chlorophenoxy)- xxxxxxxx xxxx bcnzimidazolc 2.4,6-trichloro-7-(2,4'.5'-trichloro xxxx xxxxxxx phcnoxy)hennzimidazolc 2.4.6-trichloro-7-(4'-chloro-5-trixxxx xxxxxxxx fluoromcthyl-phenoxyl-benzimidazolc EXAMPLE 9 -Continued Because oftheir good insecticidal, acaricidal and microbiocidal properties, thefollowing 2-trifluoromethyl benzimidazoles are particularly well suitedfor the combatting of insects, insect larvae, spiders and larval stagesthereof, microorganisms (bacteria and fungi) in plant protection, storesprotection and, in particular, for the protection of material:

2-trifluoromethyl-4-(3',4'-dichlorophenoxy)-5,7dichlorobcnzimidazoleM.P. 116 1182-trifluoromethyl-4-(4-chlorophenoxy)5.7-dichloro-bcnzimidazole. M.P.205 207 2 triflu0mmcthyl 4-( 2'.4 '-dichloruphcnoxy )-5.7-dichlorohcnzimiduzolc M.P.l94 1962-trifluommcthyI-4-phcnoxy-5.7-dichlorobcnzimiduzole MP. 204 2062-trifluoromcthyl-44 3 '-trifluoromcthyl-4-chlorophcnoxy )-5 ,7-dichloro-hcnzimidazole, MP. 199 201Z-trifluoromethyl-4-phenylthio-5-7-dichlorobenzimidazole. MP. 177 1792-trifluoromcthy|-4-(4'-chlorophenylthio)-5.7-dichlorobcnzimidazolc, VMP. 218 2202-trifluoromethyl-4(4"chl0rophenylsulfinyl)-5.7-dichlorobenzimidazole.2-trifluoromcthyl-4-(4'-chlorophcnylsulfonyl)-5,7-dichlorobcnzimidazole,M.P. 238 240'2-trifluoromcthyl-4-(4'-chlorophenoxy)-5,7-dichloro-6-bromobcnzimidazole,2-trifluoromethyl-4-( 3,4dichlorophcnoxy)-5,6,7-trichl0robcnzimidazole.2-trifluoromethyl-4-(4'-bromophenoxy)-5,7-dichlorohenzimidazole, M.P.20l 2032-trifluoromethyl-4-(4'-bromophcnoxy)-5,7-dichloro-6-bromobenzimidazole,2-trifluoromethyl-6-(3',4'-dichlorophcnoxy)-5-chloro-benzimidazolc,2-trifluoromethyl-6-(4'-chlorophenylthio)-5-chloro-benz imidazole.2-trifluoromethyl-6-(4'-chlorophenylsulflnyl)-5-chlorobcnzimidazolc.2-trifluoromcthyl-6-(4'-chlorophenylsulfonyl)7-5-chlorobenzimidazolc,2-trifluoromethyl-6-(3,4-dichlorophenoxy)-4,5,7-trichloro-henzimidazole.2-trifluoromethyl-6-(4'-chlorophenylthio)-4,7-dibromobcnzimidazole,2-trifluoromcthyl-6-(4'-chlorophenylsulfinyl)-4,7-dibromoS-chloro-bcnzimidazole.2-trifluoromethyl-6-(4'-chlorophenylsulfonyl)-4,7-dibromo-Schloro-benzimidazole.2-trifluoromcthyl6-(4'-bromophenoxy)-5-chloro-benzimidazolc.2-trifluoromethyl-6-(4'-bromophenoxy)-5-chloro-benzimidazolc,2-trifluoromethyl-6-(3'-trifluoromethyl-4'-chlomphenoxy)-S-chlorobenzimidazole,2-trifluoromethyl-4-(3,4-dichlorophenoxy)-5,7-dichloro-6-methyl-benzimidazolc,2-trifluoromcthyl-4-(4'-chlorophcnoxy)-5-fluoro-benzimidazolc,2-trifluoromcthyl-4-(3'-chlorophenoxy)-5,7-dichloro-benzimidazolc. M.P.I l92 -Continued e.g. the polyvalent resistent and normally sensitivehouse flies (Musca domestica), stable flies (Stomoxys calcitrans) andmosquitoes (e.g. Aedes aegyptii, Culex 5,7-dichloro-bcnzimidazolc M.P.I98 200 2-trifluuromcthyl-4(3-triflu0rnmcthylphcnoxy} fatigans,Anopheles stephensz). on insects ofthe familles I 177 5 Curculionidae,Bruchidae, Dermestidae, Teneb- 2-tr|fluoromcthyl-4(4'-chloro-3-tr|fIuoro-mcthyl- .d d Ch [2d .1 S.

phcnylthio)-5,7-dichloro-henzimidazole M.P. 175 177 ae an rysome lgranary Z-trifluoromcthyl-S-phenylthio-6chlorophilus granaria), beanbeetles (Bruchidius obtectus),

benzimidazolc M.P. 222 224 2-trifluoromcthyl-(3'-trifluoromcthyl-4'-chlorolarder beetles .(Derniesles VulpmuS)yellow meal phcnoxy)-6-chloro-bcnzimidazolc M.P. 263 265 rm (Tenebrlo lColorado potato beetles Y P Y" l0 (Leptinotarsus decemlineata) and theirstages of develazolc M.P. 205 207 h P l.d.d f .l M d.2-trifluoromcthyl-4-(4'-mcthoxyphcnoxy) 5.7- p on t e yral 1 216 drmlterranean dichloro-benzimidazolc M.P. I86 188 flour moths (Ephesliakuhniella), the Blatt1dae fam1ly,2-trifluorornethyI-4-(2,45"trichlorophenoxyy 5Idichlomhcnzimiduzolc MIR(F1520 e.g. German cockroaches (Phyllodromia gerrnamca),2-trifluoromethyl 5-(3'.4'-dichlorophcnoxy)- the Aphtdidae fam1ly, e.g.bean aphids (Aphzs fabae) 238 l5 and the Pseudococcidae family, e.g.citrus mealybugs 2-trifluoromclhyl-5-(3'-tr|fluoromethyl-4-chloro- P] HT b h.d A h. b phenylthio)-6-chloro-bcnzimidazolc M.P. 208 210 anocauusests on ean ap l S ls fa a8 2-trifluoromethyl-5-(4'-chlorophenylthio-6-and desert locusts (Schistocerca gregaria) mdicate thatchloro-benzimidazole M.P. 212 214 2 triflwmmmhyl 5 (2,'4,vs,trichlomphcnoxy) the substances have an excellent systemic act1on. They-chloro-bcnzimidazole MP. 225 227 have also a good action againsttermltes. The active 2-triflu0romcIhy|-5-(2'5dichlorwphcnyllhiolsubstances of general formula VI can be used asinsecti- -chloro-hcnzimidazolc M.P. 182 184 f l t t t f t d f2-trifluoromcthyl-5-(4'-chlorophcnoxy)6- cl eh or pro cc F pro 0 S Oresan f chloro-bcnzimiduzole P. 191 193 the protection of orgamc materialsof all types. In addi- 'gm'g gz sgzljgg P 178 tion, the activesubstances have a good action against2-trifluoromcthyl-5-(3-trifluoromcthyl-phcnoxy)- the larval and adultstages of spiders, e.g. the Tetrany- 6-chloro-bcnzimidazolc M.P. 191 193Chidae f il 2-trifluoromcthyl-5-(4bromophenoxy)- 6 Ch|0m bcnzimidamlc196 As has already been said, the new benzlmldaaoles of2-trifluoromcthyl-443,4'-dichloro-phcnoxy)- 140 general formula VI havean excellent 1nsect1cldal ac- 5,6,7-trichloro-henzimiduzolc(decomposition) i a ainst insects which d b satin i2-trifluoromcthyl-4-(3-trifluoromcthylg y y p 4' hl h lf l) 5 6"] (ri.larly agamst the larvae of Insects wh1ch eat keratin chlom-bwlimidflmle254 fibres such as moth larvae, other small butterflies, fur and carpetbeetles. The affinity of the active substances Tests of the action ofthe new compounds on insects to the keratin fibres is excellent so thatthey are most and spiders showed that these active substances aresuitable for the protection of crude and processed keragood to very goodcontact and stomach poisons and, at tin material such as wool and otheranimal hair, wool the same time they have a marked systemic action. Atextiles of all types, fells and furs, from injury by such fewbenzimidazoles of the general formula VI have insects. A goodinsecticidal protection is given to the good herbicidal properties andcan thus also be used treated materials by the active substances. forinfluencing plant growth. The insecticidal activity of2trifluoromethylben [t has been found that the compounds of the generalzimidazoles is determined according to the same test as formula VI haveexcellent protracted action on insects described in the foregoingparagraphs. The test results of the families Muscidae, Stomoxidae andCulicidae, are given a follows:

Compounds Moths Attzigcnus AnthrenusZ-trlfluoromcthyl-4-phcnoxy-5,7dichlorobcnzimidazolc -llll- -+lll- -lH-+2-trifluoromethyl-4 (2'.4'dichlorophcnoxy)-5,7-dichlorobenzimidazole-H-ll -HH- llll- Z-trifluoromethyl-4phenylthio-5,7-dichlorobenzimidazole -H-H- -l-Hl- +l-H2-trifluoromethyl-4-(4'-chlorophenylthio)-5,7-dichloro-benzimidazole HH-HH- -H-H- 2-trifluoromethyl-4-(4'-chlorophenoxy)-5,7-dichloro-benzimidazole -l-Hl -l-Hll-l-H-2-trifluoromethyl-4-(3'-chlorophenoxy)- 5,7-dichloro-benzimidazole -l-Hl-H-H- +H-l- 2-trifluoromethyl-4-(4'chl0ro-3-trifluoromethyl)-5,7-dichloro-benzimidazole -l-H+ -HH- -ll-l+2-trifluoromethyl-4-(2',5-dichlorophenylmercapto-S,7-dichloro-benzimidazole+1-44- +1+1- +1-1-1- 2-trifluoromethyl-4-(4' bromo-phenoxy)-5,7-dichloro-benzimidazole -HH- -lH-l- -Hll2-trifluoromethyl-5-(phenylmercapto) 6chloro-benzimidazole -lllll-H-l-2-trifluoromethyl-4-(3'-trifluoromethylphenoxy)-5,7-dichloro-benzimidazole-llll- -lH-l +t+l-2-trifluoromethyl-4-[4'-chloro-3'-trifluoromethyl)-phenyl-thio]5,7-dichlorobenzimidazole-Hll- -Hll- HH-2-trifluoromcthyl-5-(3-trifluoromcthyl-4-chloro-phenoxy)-6-chlorobcnzimidazole-H-H- -lH-+ HH- 2trifluoromethyl-5-phenoxy-6- chloro-benzimidazole HH-4+ -HH-2-trifluoromethyI-4-(4'-methoxyphenoxy)5,7-dichloro-benzimidazole -HH--lll-+ Continued Attagenus Anthrenus In the agar incorporation testworked out by Leonard and Blackford, (testing of bacteria and fungi onagar into which the active substances have been incorporated in variousconcentrations). the new benzimidazoles show an excellent prohibition ofgrowth of microorganisims such as bacteria, e.g. gram positive and gramnegative bacteria. and fungi, e.g. Aspergillus niger. Penicilliumitalicum. Fusarium oxysporum, Candida albicans. Acrostalagmus spec.etc., so that they are particularly suitable for the protection oforganic materials of all types from destruction and damage by bacteriaand fungi. Keratin materials such as skins, leather, wool. as well asmaterials based on cellulose such as wood, cellulose. paper. cotton,also preparations such as pastes, printing thickeners made from starchand cellulose derivatives. oils of all types, treatment liquors forpaper and textiles, plastics and synthetic materials of all types etc.are given not only insecticidal but also microbicidal protection bytreatment with the new active substances.

The active substances to be used according to the invention can be usedor combined with other known active substances. They can be combined.e.g. with halogenated salicylic acid alkylamides and alkylanilides, withhalogenated diphenyl ureas. with halogenated phenoxydiphenyl ureas, withhalogenated benzoxazoles or benzoxazolones, with 2-chloromethylsulphonylamino polychlorodiphenyl ethers, withpolychlorohydroxydiphenyl methanes, with halogen dihydroxydiphenylsulphides, with halogenated hydroxydiphenyl ethers, with bacterialcidal2- imino-imidazolidines or 2-imino-tetrahydropyrimidines or withbactericidal quaternary compounds or with certain dithiocarbamic acidderivatives such as with tetramethyl thiuram disulfide. In admixturewith synergists and auxiliaries having a similar action such as succinicacid dibutyl ester, piperonyl butoxide, olive oil, peanut oil etc., theinsecticidal and acaricidal range of action of the active substancesmentioned is widened and their action is improved. Also, theinsecticidal action can be substantially improved, broadened and adaptedto given circumstances by the addition of other insecticides such asphosphoric, phosphonic, thiophosphoric or dithiophosphoric acid estersand amides, other carbamic acid esters, halogenated hydrocarbons, DDTanalogues. pyrethrins and synergists thereof.

The new active substances are applied in the form of solid or liquidagents such as dusts, sprinkling agents, granulates, aqueous dispersionswhich are obtained from wettable powders, pastes or emulsionconcentrates, and also as solution or aerosol. For the protection oforganic materials, the active substances are brought into the mostfinely distributed form as dispersions or solutions of active substance.

The agents according to the invention are produced in the known way byintimately mixing the active substances with solid or liquid carriersand distributing agents. For the protection of material, particularlyorganic solvents have proved valuable such as: propylene glycol,methoxyethanol, ethoxyethanol and dimethyl formamide. As distributingagents, emulsifying agents, e.g. sulfated castor oil, sulfite wasteliquor and fatty alcohol surfaces can be used. The concentration ofactive substance in the agents is, e.g. 0.01 Also other biocidal activesubstances for use in plant protection also fertilisers and traceelements can be added to the agents according to the invention.

Keratin materials can be impregnated with the active substances by themost varied textile finishing processes such as hot or cold, aqueousdye, bleaching, chroming, pad dyeing or after-treatment baths. The newactive substances are fixed excellently onto the keratin fibre not onlyby hot application but also by cold application. Even after coldapplication, the new active substances have high grade wet fastnessproperties, e.g. fastness to washing and milling.

Because of the solubility in organic solvents, the active substances arealso well suitable for application from non-aqueous media. Here, thematerials to be protected can simply be impregnated with the solution.With a suitable choice of solvent, the materials can be given aninsecticidal and microbicidal finish also in a dry cleaning process.

Forms of compositions are described in the following text in which theactive substances can be used in plant protection and for the protectionof keratin materials. Dust To produce a 10% dust,

10 parts of 2-trifluoromethyl-4-phenoxy-5,7-

dichlorobenzimidazole,

5 parts of highly dispersed silicic acid and parts of talcum areintimately mixed. Such a dust can be used, e.g. for combatting Germancockroaches and ants. Wettable powder To produce (a) a 50% and (b) a 10%wettable powder, the following components are used:

50 parts of 2-trifluoromethyl-4-(3-trifluoromethyl-4-chlorophenoxy)-5,7-dichloro-benzimidazole parts of oleyl methyltauride Na salt 2.5 parts of dinaphthalene methane disulphonic aciddisodium salt 25 parts of lime/clay silicates 17.5 parts of kaolin.

parts of2-trifluoromethyl-6-(4'-chlorophenylsulfinyl)-5-chloro-benzimidazole 3parts ofa mixture of sodium salts of saturated fatty alcohol sulfonates(fatty alcohols C -C,

5 parts of dinaphthalene methane disulphonic acid disodium salt 82 partsof kaolin.

The amounts of active substance mentioned are intimately mixed insuitable mixers with the additives and the mixture is milled incorresponding mills and drums. A wettable powder is obtained which canbe diluted with water to form suspensions of any concentration desired.Such suspensions are mainly used for combatting insects in plantprotection.

Emulsion concentrate To produce (a) a 50% and (b) a 25% emulsionconcentrate, the following components are mixed together:

a. 50 parts of 2-trifluoromethyl-4-(3,4-

dichlorophenoxy)-5,7-dichloro-benzimidazole 17.5 parts of2-methoxyethanol 225 parts of xylene 8 parts of nonylphenol/polyglycolether condensate 2 parts of dodecyl benzene sulfonate calcium salt.

10 parts of 2-trifluoromethyl-4-)-bromophenoxy)-5,7-dichloro-benzimidazole 25 parts of diacetonyl alcohol 2 parts ofalkylaryl polyglycol ether 3 parts of a combination emulsifying agent(nonylphenolpolyoxyethylene-dodecyl benzene sulfonic acid calcium salt)60 parts of xylene.

These concentrates can be diluted with water to form emulsions of anyconcentration desired. Such emulsions are used. e.g. to combat insectsin plant protection and the protection of stores.

Paste To produce a 45% paste, the following substances are used:

45 parts of 2-trifluoromethyl-4-(4-chlorophenylsulfonyl)-5,7-dichlorobenzimidazole,

5 parts of sodium aluminum silicate 14 parts of cetyl polyglycol ether(condensate from saturated C C fatty alcohols and 8 mols of ethyleneoxide) 1 part of oleyl polyglycol ether (oleyl alcohol 5 mols ofethylene oxide condensate) 2 parts of spindle oil 10 parts ofpolyethylene glycol ether (Carbowax") 23 parts of water.

The active substance and the additives are intimately mixed and milledin suitable apparatus. A paste is obtained from which, by dilution withwater, suspensions of any desired concentration can be produced.

Agents according to the invention for combatting insect larvae whichinjure keratin fibers and the use of these agents for the protection ofkeratin materials from injury by such pests are further illustrated inthe following examples. Parts are given therein as parts by weight andthe temperatures are given in degrees Centigrade.

EXAMPLE 1 0.5 Parts of 2-trifluoromethyl-4-(3', 4'-dichlorophenoxy)-5,7-dichloro-benzimidazole, in the form of the sodiumsalt, are dissolved with the help of 0 10 parts of 0.1 N sodiumhydroxide solution and a little EXAMPLE II First, a 20% solution of2-trifluoromethyl-4-(3,4- dichlorophenoxy)-5,7-dichlorobenzimidazole inglycol monomethyl ether is produced, 10 parts by volume of this solutionare diluted with 200 parts by volume of a solvent suitable for drycleaning, e.g. a suitable benzine fraction (Diluan S"). If desired,additives which promote cleansing can be added, The wollen articles arethen treated in the usual way in this cleaning liquor and thencentrifuged to a solvent content of about I007: of the weight of thewool. After drying. they prove to be mothprool'.

In an analogous manner, the same baths or those of analogous compositioncan also be used for mothproofing untreated articles or articles whichhave already been treated in some way or cleaned.

Similar mixtures can also be used for sprinkling on or spraying wool inany stage of processing.

EXAMPLE [II To apply 2-trifluoromethyl-4-(3',4'-dichlorophenoxy)-5,7-dichloro-benzimidazole. the following process, forexample. can be used:

05 Parts of active substance are dissolved in 10 parts of dimethylformamide and the solution is poured into 3000 parts of water containingabout l2 parts of an wherein one of Y, and Y is nitro and the other oneis hydrogen or halogen; Z is halogen; R is trifluoromethyl, methoxy,chlorine or bromine; m is an integer of from 0 to 5; and p is an integerof from O to 2.

A Compound of the formula m is an integer of from O to 5; and

p is an integer of from to 2. I 3. A compound according to claim 1,wherein at least 1 Z one of Y Y and Z is halogen.

5 4. A compound according to claim 2 which is 3,5-dichloro-6-(4-chlorophenoxy)-1,Z-phenylenediamine.

2 5. A compound according to claim 2 which is 3,5-dichloro-6-(2,4-dichlor0phenoxy)-l.2-

m l0 phcnylenediamine.

6. A compound according to claim 2 which is 3,5- hdichloro-6-(2,4',5'-trichlorophenoxy)-l,2- w erem I I Iphenylenediamine.

one of and Y2 ls ammo and the other one Is 7. A compound according toclaim 2 which is 3,5- or halogen;dichloro-6-(3-trifluoromethyl-4-chlorophenoxy)l,2- 2 IS or halogen"phenylenediamine. R is trifluromethyl, methoxy, chlorine or bromine;

1. A COMPOUND OF THE FORMULA
 2. A COMPOUND OF THE FORMULA2-Y1'',3-(H2N-),4-Y2'',(Z)P,(R)M-DIPHENYL ETHER WHEREIN ONE OF Y1 AND Y2IS AMINO AND THE OTHER ONE IS HYDROGEN OR HALOGEN, Z IS OR HALOGEN, R ISTRIFLUROMETHYL, METHOXY CHLORINE OR BROMINE, M IS AN INTEGER OF FROM 0TO 5 AND P IS AN INTEGER OF FROM 0 TO
 2. 3. A compound according toclaim 1, wherein at least one of Y1, Y2 and Z is halogen.
 4. A compoundaccording to claim 2 which is3,5-dichloro-6-(4''-chlorophenoxy)-1,2-phenylenediamine.
 5. A compoundaccording to claim 2 which is 3,5-dichloro-6-(2'',4''-dichlorophenoxy)-1,2-phenylenediamine.
 6. A compound according toclaim 2 which is 3,5-dichloro-6-(2'',4'',5''-trichlorophenoxy)-1,2-phenylenediamine.
 7. A compound accordingto claim 2 which is3,5-dichloro-6-(3''-trifluoromethyl-4''-chlorophenoxy)1,2-phenylenediamine.